Process of producing fast dyeings and the dyed fiber obtained thereby



Patented July 23, 1

UNITED ST TES PATENT OFFICE PROCESS OF PRODUCING FAST DYEINGS AND THEDIED FIBER OBTAINED THERE- No Drawing.

Application February 11, 1939, Se-

No. 255,958. In Germany February 17,

10 Claims.

The present invention relates to a process of producing fast dyeings andto the dyed flber obtained thereby.

We have found that valuable dyeings on cellulose esters and ethers or onhydrophilic artificial highly polymeric bodies, of all kinds, such asfabrics, sheets, moulded articles or latices may be obtained by applyingto the highly polymeric body, in an aqueous neutral, acid or alkalinesolution or suspension, a condensation product free from sulfonic acidgroups, containing a heterocyclic ring, an amino-group capable of beingdiazotized and a hydroxyl group rendering }5 the coupling possible, andthen diazotizing the compound. The self-coupling of the diazo-compoundof the amino-hydroxy compound frequently occurs spontaneously; ingeneral, however, it is brought about or completed by a treatment withan agent neutralizing the acid or having an alkaline action.

By the new process it, is, for instance, possible to dye directly sheetsfrom acetyl-, ethylor benzyl-cellulose or from polymerization productsthe most various shades. Besides the hitherto unknown possibility ofdyeing sheets, moulded articles or latices, it is also possible toobtain on fabrics, from the above highly polymeric bodies, particularlyacetate silk or acetate silk staple fiber dyeings of good properties of.fastness, the highly polymeric character .of the body being preserved.

As condensation products of theabove-mentioned composition theremay, forinstance,-be 35 used the following compounds:

Amino-hydroxy-styryl-quinolines, Amino-aryl-pyrazolones,Amino-hydroxy-benznaphthoxazoles, Amino-hydroxy-naphthobenzoxazoles,Amino-hydroxy-phenylbenzoxazoles, Amino-hydroxy-benznaphthothiazoles,Amino-hydroxy-naphthobenzthiazoles, Amino-hydroxy-phenylbenzthiazoles,Amino-hydroxy-benznaphthimidazoles, Amino-hydroxy-naphthobenzimidazoles,Amino-hydroxy-phenylbenzimidazoles, Amino -arylbarbituric acid. a

The following examples serve to illustrate the 50 invention, but theyare not'intended tolimit it thereto: v i

l. 1 kilo of acetate silk yarn is treated for one hour at 85 C., with asuspension in 25 liters of water of 30 grams of finely divided4-aminobenzal-3-hydroxy-quinaldine l3 hydroxy-2-(4'aminostyryD-quinolinel of the following constitution:

CH=CH N (obtained by condensing 3-hydroxy-quinaldine withparanitrobenzaldehyde in a manner analogous to that described inBerichte der deutschen Chemischen Gesellschaft, volume XX, page 2046,and subsequently reducing the nitro-group). The yarn is then centrifugedand introduced into a batch containing per 30 liters of cold water 30grams of sodium nitrite and 80 cc. of concentrated hydrochloric acid.

After one hour, the diazotization is complete. The material is againcentrifuged and then developed in a bath containing 30 liters of coldwater and 80 cc. of ammonia of 25 per cent strength. Thereupon, thematerial is centrifuged and dried. A deep black dyeing of good fastnessto-rubbing and washing is obtained.

Instead of hydrochloric acid there may be used for the diazotizationother inorganic acids, such as, for instance, sulfuric acid, orpreferably organic acids, such as acetic acid or formic acid.

2. 1 kilo of a sheet prepared from acetyl-cellulose is, according to itsthickness, treated, for 1 to 2 hours at 85 C. with a solution containingper 50 liters of water 20 grams of 1-(3'-aminophenyl)-3-methyl-5-pyrazolone and then introduced into a bath containing per 50liters of water 20 grams of sodium nitrite and 80cc. of formic acid of85 per cent strength. The base, which has been taken up by the foil is,thereby, diazotized and, for the main part, coupled with itself. After 1to 2 hours, the diazo-solution is run off, and 50 liters of fresh waterand 50 cc. of ammonia of 25 per cent strength are then added. The sheet,which has been dyed a uniform yellow tint ls rinsed with water anddried.

In the same manner, a sheet from ethyl-cellulose is dyed a uniformyellow tint.

3. 1 kilo of an aqueous emulsion of about 50 per cent strength ofpolyvinyl acetate is intimately mixed with a solution containing per 100cc. of hot water 10 grams of 1-(3'-aminopheny1)- 3-methyl-5-pyrazoloneand the whole is heated to 50 C. to 60 0.; nitrous acid gas is thenintroduced. The base is thus diazotized, self-coupling simultaneouslyoccurring and a yellow dyestuif being formed. As soon as the depth ofcolor of the emulsion no longer increases, the introduction of gas isinterrupted and the excess of nitrous acid is removed by introduction orair. A yellow emulsion is thus obtained which may be further worked upin the usual manner.

The following table illustrates a. number of other dyeings obtainable byself-coupling according to the present invention:

Parent material Shade OH-OH N obtainable by condensing3-hydroxyquinaldine with meta-nitmbenraldeh de in a manner analogous tothat described in erichte der Deutschen Chemischen Gesellschait," volumeXVI, page 2000, and subsequenti reducing the nitro-grou 2. l- 4'-aminopenyl)-3-meth?l-5-pyrazo one 3. 1- '-amino-6-chloropheny)-3-methyl-5-pyrazolone...

- obtainable by condensing para-nitrobenzoylchloride withl-amino-ZJ-dihydroxynaphthalene and subsequently reducing thenitro-group.

*uiQ,

Brown.

0 range. Yellow.

Ited.

Scarlet.

obtainable by reducing meta-nltrophenyl-Mrydroxy- N-(D-naphthoxazole,which is prepared by condensing metanitrobanzoyl chloride with1-amino-2.5- dlhydroxynaphthalene.

Brownorange.

obtainable by reducing the condensation product trom meta-nitro-cinnamicacid chloride and 1.2- diaminoa'i-hydroxynaphthalene.

Brown.

obtainable by reducing the condensation product from para-nitro-cinnamicaldehyde and 1.2-diamin hydroxy-naphthalene.

NH Cl N N NE,

obtainable by condensing 2.3-hydroxynaphthoic acid chloride with 2.4dinitro-chloro-l-aniline, and subsequently reducing the nitro-groups,the imidazole being simultaneously formed.

Blueish red.

Parent material Shade obtainable by condensing 2.3hydro1'ynaphthoic acidchloride with 1.2-diamino-4-nitroben1-ene and reducing thenitro-imidazole derivative formed.

N NE:

obtainable by condensing 2.3-hyrdoxynapbthoic acid chloride with2-an1ino-4-nitro-1-hydrorybenzene, and subsequently reducing thenitro-group.

Red.

(JO-CH:

HIN N\ /C O O O-NH obtainable by condensing paranitrmiaphenyl urea withmalonic acid and subsequently ucing the nitrogroup.

Orange.

We claim:

1. The process which comprises applying to materials of the groupconsisting of cellulose esters and ethers and hydrophilic artificialhighly polymeric bodies, in an aqueous medium, an aminoaryl-pyrazoloneof the following constitution:

wherein X stands for a member of the group consisting of hydrogen andhalogen, then diazotizing the compound on the material and causing thediazo-compound to combine with itself.

2. The process which comprises applying to materials of the groupconsisting of cellulose esters and ethers and hydrophilic artificialhighly polymeric bodies, in an aqueous medium, an aminoaryl-pyrazoloneof the following constitution:

x-- NH:

aminoaryl-pyrazolone oi the following constitution:

wherein X stands for a member of the group consisting of hydrogen andhalogen, then diazotizing the compound 'on the material and causing thediam-compound to combine with itself by passing the diazotized goodsthrough a. bath having an alkaline action subsequently to thediscotization process. 4

4. The process which comprises applying to cellulose esters, in anaqueous medium, 1-(3'- aminophenyl) -3-methy1-5-pyrazolone, thendiazotizing the compound on the fiber and causing the diazo-compound tocombine with itself by an alkaline treatment.

5. The process which comprises applying to cellulose esters and ethersdyed with an ace-- compound obtainable on the fiber by the processclaimed in claim 1.

'l. Fibrous material of the group consisting oi cellulose esters andethers dyed with an azocompound obtainable on the flber by the processclaimed in claim 2.

8. Fibrous material of the group consisting of cellulose esters andethers dyed with an azocompound obtainable on the fiber by the processclaimed in claim 3.

9. Fibrous material or the group consisting o! cellulose esters andethers dyed with an azucompound obtainable on the fiber by the processclaimed in claim 4.

10. Fibrous material of the group consisting of cellulose esters andethers dyed with an azo-compound obtainable on the fiber by the processclaimed in claim 5.

GEORG mlinzmm. WERNER KIRST. CARL JOSE]? mm

